We performed reaction path search calculations for the NaCl·(H2O)6 cluster using the global reaction route mapping (GRRM) code to understand the atomic‐level mechanisms of the NaCl → Na+ + Cl− ionic dissociation induced by water solvents. Low‐lying minima, transition states connecting two local minima and corresponding intrinsic reaction coordinates on the potential energy surface are explored. We found that the NaCl distances at the transitions states for the dissociation pathways were distributed in a relatively wide range of 2.7–3.7 Å and that the NaCl distance at the transition state did not correlate with the commonly used solvation coordinates. This suggests that the definition of the transition states with specific structures as well as good reaction coordinate is very difficult for the ionic dissociation process even in a small water cluster. © 2018 Wiley Periodicals, Inc.

中文翻译：

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关于小NaCl·(H2 O)6簇中离子对解离机制：反应路径搜索计算的视角

我们使用全局反应路线图 (GRRM) 代码对 NaCl·(H2O)6 簇进行了反应路径搜索计算，以了解水溶剂诱导的 NaCl → Na + + Cl− 离子解离的原子级机制。探索了低势极小值、连接两个局部极小值的过渡态和势能面上相应的内在反应坐标。我们发现解离途径过渡态的 NaCl 距离分布在 2.7-3.7 Å 的相对较宽的范围内，并且过渡态的 NaCl 距离与常用的溶剂化坐标无关。这表明即使在小水簇中，离子解离过程也很难定义具有特定结构和良好反应坐标的过渡态。© 2018 Wiley Periodicals, Inc.